Substrate, in particular glass substrate, supporting at least one stack of a photocatalytic layer and a sublayer for the heteroepitaxial growth of said layer

ABSTRACT

The invention relates to a structure, comprising a substrate supporting a layer with a photocatalytic and anti-soiling property on at least part of the surface thereof, said layer being based on titanium dioxide (TiO 2 ) which is at least partially crystallized in the anatase form thereof. Said structure is characterised in comprising a sublayer (SC) directly under at least one TiO 2  layer, said sublayer having a crystallographic structure which provides assistance to crystallization by heteroepitaxial growth in the anatase form of the TiO 2 -based upper layer, the photocatalytic property being obtained without any heating step.

The present invention relates to substrates, such as glass, glass-ceramic or plastic substrates, which have been provided with a photocatalytic coating in order to give them what is called an “antisoiling or self-cleaning” function.

One important application of these substrates relates to glazing, which may be applied in very many different situations—from utilitarian glazing to glazing used in domestic electrical appliances, from automotive glazing to architectural glazing.

It also applies to reflective glazing of the mirror type (domestic mirrors or driving mirrors) and to opacified glazing of the lightened type.

Similarly, the invention also applies to nontransparent substrates, such as ceramic substrates or any other substrate that may in particular be used as architectural material (metal, tiling, etc.). Preferably, it applies, irrespective of the nature of the substrate, to substantially flat or slightly curved substrates.

Photocatalytic coatings have already been studied, especially those based on titanium oxide crystallized in anatase form. Their capability of degrading soil of organic origin or microorganisms through the action of UV radiation is very beneficial. They also often have a hydrophilic character, allowing mineral soil to be removed by spraying it with water or, in the case of outdoor glazing, by rain.

This type of coating exhibiting antisoiling, bactericidal or algicidal properties has already been described, for example in Patent WO 97/10186, which describes several embodiments thereof.

To exert its antisoiling function (hydrophilicity and destruction of organic contaminating chains), the TiO₂ must be at least partly crystallized in the anatase structure. Otherwise TiO₂ is not functional and requires a heat treatment after deposition, so as to acquire the crystallographic structure that makes it effective.

Thus, if the TiO₂ is deposited by a chemical vapor deposition (CVD) technique involving a high temperature, it has the correct structure spontaneously. If it is deposited cold (at room temperature), especially by a vacuum deposition technique, it becomes functional only after a suitable heat treatment.

The object of the present invention is to propose a solution for obtaining the correct state of TiO₂ without employing a heating step. However, such a heating step (toughening or annealing operation), envisaged in certain cases such as for safety applications or applications in which the surface of the glass has to be hardened, is not excluded.

For this purpose, the present application proposes the deposition, just before deposition of the TiO₂ layer, of an underlayer that will provide an appropriate base for correct growth of the TiO₂ layer (heteroepitaxial growth), this underlayer being advantageously deposited at room temperature and without requiring the substrate to be heated either.

International Application WO 02/40417 describes the deposition of a ZrO₂ underlayer followed by TiO₂ under very many possible conditions, with the need for heating, without the preferential formation of anatase being demonstrated, the rutile form also being favored.

The first subject of the invention is therefore a structure comprising a substrate bearing, on at least part of its surface, an antisoiling layer having a photocatalytic property, based on titanium dioxide (TiO₂) at least partly crystallized in its anatase form, characterized in that it includes, immediately beneath at least one TiO₂ layer, an underlayer (UL) having a crystallographic structure that has assisted in the crystallization, by heteroepitaxial growth in the anatase form, of the TiO₂-based upper layer, the photocatalytic property having been acquired without any heating step.

The underlayer (UL) is in particular based on a compound crystallized in a cubic or tetragonal system and having a lattice cell dimension equal to that of TiO₂ crystallized in anatase form to within ±8%, especially to within ±6%.

Preferably, the underlayer (UL) consists of ATiO₃, A denoting barium or strontium.

The thickness of the underlayer (UL) is not critical. For example, thickness values of between 10 and 100 nm may be mentioned.

The substrate consists, for example, of a sheet, whether plane or with curved faces, of monolithic or laminated glass, glass-ceramic or a hard thermoplastic, such as polycarbonate, or else consists of glass or glass-ceramic fibers, said sheets or said fibers having, where appropriate, received at least one other functional layer before application of the underlayer (UL) (in the case of more than one layer, this may also be referred to as a multilayer stack).

The applications of the sheets were mentioned above. As regards the application of the fibers, mention may be made of air or water filtration, and also bactericidal applications.

If the substrate is made of glass or glass-ceramic, at least one functional layer subjacent to the underlayer (UL) may be a layer forming a barrier to the migration of alkali metals from the glass or glass-ceramic. Such migration is liable to result from the application of temperatures in excess of 600° C. Such layers forming a barrier to alkali metals are known, and mention may be made of SiO₂, SiOC and SiO_(x)N_(y) layers, with a thickness for example of at least 50 nm, as described in PCT International Application WO 02/24971.

At least one functional layer subjacent to the underlayer (UL) may be a layer having an optical functionality (advantageously for adjusting the optics in reflection), a thermal control layer or a conducting layer.

The layers having an optical functionality are especially antireflection layers, light radiation filtration layers, coloration layers, scattering layers, etc. Mention may be made of layers consisting of SiO₂, Si₃N₄, amorphous TiO₂, photocatalytic crystallized TiO₂, SnO₂, ZnO.

The thermal control layers are especially solar control layers or what are called low-e (low-emissivity) layers.

The conducting layers are especially heating layers, antenna layers or antistatic layers, and arrays of conducting wires may be included among these layers.

To give an example, mention may be made of glass or glass-ceramic substrates, especially of the sheet type, that have received a layer acting as a barrier to the migration of alkali metals from the glass or glass-ceramic, followed by a monolayer, bilayer or trilayer having an optical functionality.

The TiO₂ base layer consists of TiO₂ alone or of TiO₂ doped with at least one dopant chosen in particular from: N; pentavalent cations such as Nb, Ta and V; Fe; and Zr.

According to advantageous features of the present invention:

-   -   the TiO₂ layer has been deposited at room temperature by vacuum         sputtering, where appropriate magnetron and/or ion-beam         sputtering;     -   the underlayer (UL) has been deposited at room temperature by         vacuum sputtering, where appropriate magnetron and/or ion-beam         sputtering;     -   ATiO₃ has been deposited at room temperature by vacuum         sputtering, where appropriate magnetron and/or ion-beam         sputtering, using ceramic targets chosen from ATiO₃, ATiO_(3-x)         where 0<x≦3, and ATi,     -   the supply being a radiofrequency supply and the atmosphere in         the sputtering chamber containing only argon when ATiO₃ is used         as target, the supply being a DC or AC supply and the reactive         atmosphere in the sputtering chamber containing oxygen and argon         when ATi or ATiO_(3-x) is used as target,     -   the TiO₂ layer having been deposited in a following step in the         same sputtering chamber.

The TiO₂ layer may be coated with at least one overlayer of a material that does not disturb the antisoiling function of the TiO₂ layer, such as SiO₂.

The layers intended to be in contact with the atmosphere in the finished structure are, depending on the case, hydrophilic layers or hydrophobic layers.

The subject of the present invention is also the application of ATiO₃ to the formation of a layer for assisting in the crystallization, in the anatase form by heteroepitaxial growth, of an optionally doped ATiO₂-based upper layer, A denoting barium or strontium.

The subject of the present invention is also a process for producing a structure as defined above, characterized in that an ATiO₃ underlayer, A denoting barium or strontium, is deposited on a substrate made of glass or glass-ceramic or hard polycarbonate-type plastic, of the sheet type, or on glass or glass-ceramic fibers, followed by an optionally doped TiO₂ layer, at least one overlayer of a material not disturbing the antisoiling function of the TiO₂ layer then possibly being deposited where appropriate on this TiO₂ layer.

The ATiO₃ underlayer (UL) and the TiO₂ layer may be deposited in succession at room temperature by vacuum sputtering, where appropriate magnetron and/or ion-beam sputtering, in the same chamber, the targets used for depositing said underlayer being chosen from ATiO₃, ATiO_(3-x), where 0<x≦3, and ATi, the supply being a radiofrequency supply and the atmosphere in the sputtering chamber containing only argon when ATiO₃ is used as target, the supply being a DC or AC supply and the reactive atmosphere in the sputtering chamber containing oxygen and argon when ATi or ATiO_(3-x) is used as target; and the target used for depositing the TiO₂ being Ti or TiO_(x), where 0<x<2.

If the ATiO₃ is deposited by vacuum sputtering, the pressure may be between 10⁻¹ and 2.5 Pa.

If the TiO₂ is deposited by sputtering, where appropriate magnetron and/or ion-beam sputtering, the supply is generally a DC or AC supply and the pressure is advantageously about 1-3 Pa.

According to the present invention, it is possible for a heat treatment step not to be carried out after the TiO₂ layer and, where appropriate, the overlayer(s) have been deposited.

If the coating of a glass or glass-ceramic substrate is carried out, it is possible, before the underlayer (UL) has been applied, to deposit at least one layer forming a barrier to the migration of alkali metals present in the glass or glass-ceramic to be deposited on the substrate, an annealing or toughening operation then possibly being carried out, after the TiO₂ layer and, where appropriate, the overlayer(s) have been deposited, at a temperature of between 250° C. and 550° C., preferably between 350° C. and 500° C. in the annealing operation, and at a temperature of at least 600° C. in the case of the toughening operation.

The toughening or annealing operations may be carried out in cases where it will be desirable to improve the activity of the TiO₂ layer.

The possible constituents of the above barrier layers have been described above. Such layers may be deposited by sputtering, where appropriate magnetron sputtering, using known targets, (for example Al:Si in the case of an aluminum-doped SiO₂ layer), advantageously in pulsed mode, whether AC or DC, at a pressure of 10⁻¹ to 1 Pa and in gaseous argon/oxygen.

Before the ATiO₃ underlayer (UL) has been applied, at least one functional layer chosen from layers having an optical functionality, thermal control layers and conducting layers may also be deposited, said functional layers being advantageously deposited by vacuum sputtering, where appropriate magnetron and/or ion-beam sputtering.

The subject of the present invention is also single or multiple glazing comprising, respectively, one or more than one structure as defined above, both the TiO₂-based antisoiling layer and its associated underlayer (UL) being present on at least one of its external faces, the faces not having the TiO₂-based antisoiling layer and its associated underlayer possibly including at least one other functional layer. These layers may be chosen from those described above.

Such glazing is applicable as “self-cleaning” glazing, especially antifogging, anticondensation and antisoiling glazing, especially as architectural glazing of the double-glazing type, automotive glazing of the windshield, rear window and side windows of automobiles, driving mirrors, glazing for trains, airplanes and ships, utilitarian glazing, such as glass for aquariums, shop windows, greenhouses, interior furnishing, urban furniture (bus shelters, advertising panels, etc.), mirrors, screens for display systems of the computing, television or telephone type, electrically controllable glazing, such as electrochromic or liquid-crystal glazing, electroluminescent glazing and photovoltaic glazing.

The following examples illustrate the present invention without however limiting its scope.

EXAMPLE 1 (ACCORDING TO THE INVENTION) Glass/SiO₂/BaTiO₃/TiO₂ Stack

The following successive layers were deposited on a glass sheet 4 mm in thickness:

-   -   an SiO₂ layer 150 nm in thickness;     -   a BaTiO₃ layer 10 nm in thickness; and     -   a TiO₂ layer 100 nm in thickness.

The above three layers, SiO₂, BaTiO₃ and TiO₂, were deposited by magnetron sputtering under the following respective conditions:

-   -   SiO₂ layer using an Al:Si target, with a supply in pulsed mode         (change-of-polarity frequency: 30 kHz) at a pressure of 2×10⁻³         mbar (0.2 Pa), a power of 2000 W and 15 sccm of Ar and 15 sccm         of O₂;     -   BaTiO₃ layer using a BaTiO₃ target, with a radiofrequency         supply, at a pressure of 4.4×10⁻³ mbar (0.44 Pa), a power of 350         W and 50 sccm of argon; and     -   TiO₂ layer deposited using a TiO_(x), target with a DC supply,         at a pressure of 24×10⁻³ mbar (2.4 Pa), a power of 2000 W, 200         sccm of Ar and 2 sccm of O₂

EXAMPLE 2 (ACCORDING TO THE INVENTION)

The same stack as in Example 1 was produced, except that the BaTiO₃ layer had a thickness of 20 nm.

EXAMPLE 3 (COMPARATIVE EXAMPLE) Glass/SiO₂/TiO₂ Stack

The stack above was produced under the same conditions as in Example 1, except that the BaTiO₃ layer was not deposited.

EXAMPLE 4 Evaluation of the Photocatalytic Activity

The photocatalytic activity of the TiO₂ layer of each of the stacks of Examples 1 to 3, and also of the TiO₂ layer of a stack sold by Saint-Gobain Glass France under the trademark “Bioclean™”, was evaluated, the evaluation having been performed without annealing and after annealing carried out under the following conditions: rise from room temperature to 500° C. at a rate of 5° C./min; 2 hours at 500° C.; natural cooling.

The evaluation test was the stearic acid photodegradation test followed by infrared transmission, described in PCT International Application WO 00/75087.

The results are given in Table I. TABLE I SAT* without annealing SAT* after annealing Stack (×10⁻³cm⁻¹ · min⁻¹) (×10⁻³cm⁻¹ · min⁻¹) Example 1 9.7 40 (invention) Example 2 9.2 32 (invention) Example 3 1.2 35 (comparative) *Stearic acid test. 

1. A structure comprising a substrate bearing, on at least part of its surface, an antisoiling layer having a photocatalytic property, based on titanium dioxide (TiO₂) at least partly crystallized in its anatase form, wherein it includes, immediately beneath at least one TiO₂ layer, an underlayer (UL) having a crystallographic structure that has assisted in the crystallization, by heteroepitaxial growth in the anatase form, of the TiO₂-based upper layer, the photocatalytic property having been acquired without any heating step.
 2. The structure as claimed in claim 1, wherein the underlayer (UL) is based on a compound crystallized in a cubic or tetragonal system and having a lattice cell dimension equal to that of TiO₂ crystallized in anatase form to within ±8%.
 3. The structure as claimed in claim 1, wherein the underlayer (UL) consists of ATiO₃, A denoting barium or strontium.
 4. The structure as claimed in claim 1, wherein the underlayer (UL) has a thickness of between 10 and 100 nm.
 5. The structure as claimed in claim 1, wherein the substrate consists of a sheet, whether plane or with curved faces, of monolithic or laminated glass, glass-ceramic or a hard thermoplastic, or else consists of glass or glass-ceramic fibers, said sheets or said fibers having, where appropriate, received at least one other functional layer before application of the underlayer (UL).
 6. The structure as claimed in claim 5, wherein the substrate is made of glass or glass-ceramic, wherein at least one functional layer subjacent to the underlayer (UL) is a layer forming a barrier to the migration of alkali metals from the glass or glass-ceramic.
 7. The structure as claimed in claim 5, wherein at least one functional layer subjacent to the underlayer (UL) is a layer having an optical functionality, a thermal control layer or a conducting layer.
 8. The structure as claimed in claim 5, wherein the substrate is made of glass or glass-ceramic, wherein the substrate has received a layer acting as a barrier to the migration of alkali metals from the glass or glass-ceramic, followed by a monolayer, bilayer or trilayer having an optical functionality.
 9. The structure as claimed in claim 1, wherein the TiO₂ base layer consists of TiO₂ alone or of TiO₂ doped with at least one dopant selected from the group consisting of N; pentavalent cations; Fe; and Zr.
 10. The structure as claimed in claim 1, wherein the TiO₂ layer has been deposited at room temperature by vacuum sputtering, where appropriate magnetron and/or ion-beam sputtering.
 11. The structure as claimed in claim 1, wherein the underlayer (UL) has been deposited at room temperature by vacuum sputtering, where appropriate magnetron and/or ion-beam sputtering.
 12. The structure as claimed in claim 3, wherein ATiO₃ has been deposited at room temperature by vacuum sputtering, where appropriate magnetron and/or ion-beam sputtering, using ceramic targets selected from the group consisting of ATiO₃, ATiO_(3-x), wherein 0<x≦3, and ATi, the supply being a radiofrequency supply and the atmosphere in the sputtering chamber containing only argon when ATiO₃ is used as target, the supply being a DC or AC supply and the reactive atmosphere in the sputtering chamber containing oxygen and argon when ATi or ATiO_(3-x) is used as target, the TiO₂ layer having been deposited in a following step in the same sputtering chamber.
 13. The structure as claimed in claim 1, wherein the TiO₂ layer is coated with at least one overlayer of a material that does not disturb the antisoiling function of the TiO₂ layer.
 14. The application of ATiO₃ to the formation of a layer for assisting in the crystallization, in the anatase form by heteroepitaxial growth, of an optionally doped ATiO₂-based upper layer, A denoting barium or strontium.
 15. A process for producing a structure as defined in claim 1, wherein an ATiO₃ underlayer, A denoting barium or strontium, is deposited on a substrate made of glass or glass-ceramic or hard polycarbonate-type plastic, of the sheet type, or on glass or glass-ceramic fibers, followed by an optionally doped TiO₂ layer, at least one overlayer of a material not disturbing the antisoiling function of the TiO₂ layer then possibly being deposited where appropriate on this TiO₂ layer.
 16. The process as claimed in claim 15, wherein the ATiO₃ underlayer (UL) and the TiO₂ layer are deposited in succession at room temperature by vacuum sputtering, where appropriate magnetron and/or ion-beam sputtering, in the same chamber, the targets used for depositing said underlayer selected from the group consisting of ATiO₃, ATiO_(3-x), wherein 0<x≦3, and ATi, the supply being a radiofrequency supply and the atmosphere in the sputtering chamber containing only argon when ATiO₃ is used as target, the supply being a DC or AC supply and the reactive atmosphere in the sputtering chamber containing oxygen and argon when ATi or ATiO_(3-x) is used as target; and the target used for depositing the TiO₂ being Ti or TiO_(x), where 0<x<2.
 17. The process as claimed in claim 16, wherein no heat treatment step is carried out after the TiO₂ layer and, where appropriate, the overlayer(s) have been deposited.
 18. The process as claimed in claim 15, wherein the coating of a glass or glass-ceramic substrate is carried out, wherein, before the underlayer (UL) has been applied, at least one layer forming a barrier to the migration of alkali metals present in the glass or glass-ceramic is deposited on the substrate, an annealing or toughening operation then possibly being carried out, after the TiO₂ layer and, where appropriate, the overlayer(s) have been deposited, at a temperature of between 250° C. and 550° C. in the annealing operation, and at a temperature of at least 600° C. in the case of the toughening operation.
 19. The process as claimed in claim 15, wherein before the ATiO₃ underlayer (UL) has been applied, at least one functional layer selected from the group consisting of layers having an optical functionality, thermal control layers and conducting layers is deposited, said functional layers being advantageously deposited by vacuum sputtering, where appropriate magnetron and/or ion-beam sputtering.
 20. A single or multiple glazing comprising, respectively, one or more than one structure as defined in claim 1, both the TiO₂-based antisoiling layer and its associated underlayer (UL) being present on at least one of its external faces, the faces not having the TiO₂-based antisoiling layer and its associated underlayer possibly including at least one other functional layer. 